1. Technical Field
This invention relates to an aqueous coating composition such as coatings, inks, coverprint varnish and surface treatment applications containing an oxazoline or oxazine acetoacetate polymer.
2. Background Art
In the following description of the prior art and in the Examples, the parenthetical numbers are described in the following Reference section. Acetoacetamide, acetoacetanilide, and acetoacetate functionalized chemicals are readily available, via reaction of amines or hydroxyl substituted molecules with diketene (1-3), alkyl acetoacetates, or the readily used acetoacetalation compound 2,2,6-trimethyl-1,3-dioxin-4-one, which is prepared from reaction of diketene with acetone (2,4). Organic compounds or polymers with the acetoacetamide, acetoacetanilide, or acetoacetate type functionality are known to react with a variety of other functional chemicals (1-5), including such things as amines, aldehydes, and isocyanates, giving various adducts in excellent yields at low reaction temperatures (2). Also, the acetoacetamide, acetoacetanilide, or acetoacetate group, with amine catalysts, will combine readily with the acrylate functionality, via what is commonly called the Michael addition reaction (2,5,6). Further, these acetoacetanilide, acetoacetamide, or acetoacetate groups are known to readily react with various metal compounds, such as CaO, Ca(OH)2, BaO, CoCI2, NiCI2, etc. to form metal complexes (1,3), where the chemistry has been used to prepare polymeric catalysts (2,7,8) and crosslinked coatings (6,9-11). These chemicals with the acetoacetamide, acetoacetanilide, and/or acetoacetate functionality, which have three active centers, have found extensive utility in the formation of metal-complexes, manufacture of dyes and synthesis of heterocycles (1-3).
It is well known that cyclic imino ethers, such as oxazolines and oxazines will undergo cationic, ring-opening polymerizations (12) and zwitterionic copolymerization with such things as acrylic acid, maleimides, anhydrides, lactones, etc. (13-17). It is also well known that molecules with the oxazoline or oxazine residues will undergo ring-opening reactions with compounds such as carboxylic acids, thiols (HS-groups), phenols, alkyl halides, etc., giving 1-to-1 adducts (18-24), allowing for step-growth copolymerizations to be readily achieved with difunctional monomers. Further, it has been shown that alkyl halides will initiate ring-opening polymerization of cyclic imino ethers, as well as give 1:1 adducts (18, 25). Thus oxazolines and oxazines are excellent intermediates for synthesis of variety of polymeric materials, both thermoplastics and thermosets, by chain-growth and step-growth polymerization mechanisms or combinations thereof. In addition, the synthesis and polymerization of oxazoline and oxazine methacrylate aqueous coating compositions are also known (27).
1. U.S. Pat. No. 3,304,328 (Feb. 14, 1967) to FMC Corporation.
2. N. Moszner, U. Salz, V. Rheinberger, MACROAKRON ""94, 35th IUPAC Int. Symp. on Macromolecules, Jul. 11-15, 1994 paper.
3. S. M. Hussain, A. M. El-Reedy, S. A. El-Sherabasy, J. Heterocyclic Chem., 25, 9-22 (1988).
4. Wacker Chemicals (USA), Inc. literature, p. 16, 1989
5. R. J. Clemens, J. S. Witzman, F. Del Rector, Communications of Eastman Chemical Products, Inc.
6. K. J. Edgar, K. M. Arnold, W. W. Blount, J. E. Lawniczak, and D. W. Lowman, Macromolecules 1995, 28, 4122-4128.
7. T. Sato, A. Morita, I. Kamiya, T. Ota, Makromol. Chem., Rapid Comm. 11 (1990) 553.
8. R. Ran, D. Fu, J. Macromol. Sci.-Chem. A27 (1990) 625.
9. D. L. Trumbo, Polymer Bull. 26 (1991) 265,481.
10. J. R. Grawe, B. G. Bufkin, J. Coatings Technol. 52 (1980) 73.
11. U.S. Pat. No. 4,247,671 (Jan. 27, 1981) to Rohm and Haas Co.
12. S. Kobayashi and T. Saegusa, Encyclopedia of Polymer Science and Engineering, Wiley and Sons, New York, Vol. 4, pp. 525-537, 1986.
13. G. Odian, M. P. O""Callaghan, C. K. Chien, P. Gunatillake, M. Periyasay and D. L. Schmidt, Macromolecules, 23(4), 918-927 (1990).
14. C. I. Simionescu, et. al., Polymer. Bull. (Berlin), 14(1), 79-83 (1985).
15. T. Saegusa, Makromol. Chem., Suppl., 4, 73-84 (1981).
16. B. L. Rivas and G. D. Pizarro, Eur. Polym. J., 25(10), 1001-1005 (1989).
17. G. S. Canessa, A. S. Pooley, M. Parra and B. L. Rivas, Polym. Bull. (Berlin), 11(5), 465-70 (1984).
18. J. A. Frump, Chem. Rev., 71(5), 483-505 (1971).
19. U.S. Pat. No. 3,758,62, (Sep. 11, 1973), to Dow Chemical.
20. U.S. Pat. No. 4,600,766 (Jul. 15, 1986) to Takeda Chemical Co.
21. T. Nishikubo, T. Iizawa and A. Tokairin, Mackromol. Chem., 185, 1307-1316 (1984).
22. T. Kagiya, S. Narisawa, T. Maeda and K. Fukui, Polymer Letters, 4, 257-260 (1966).
23. U.S. Pat. No. 4,430,491 (Feb. 7, 1984) to Ashland Chemical Co.
24. B. M. Culbertson, M. L. Deviney, O. Tiba and D. D. Carlos, 33rd SAMPE Symp., March 7-10, pp. 1530-1545 (1988), Ibid. 34th SAMPE Symp. May 8-11, 1989. PP. 2483-2497.
25. S. Kobayashi, H. Uyama, Y. Narita and J. Ishiyama, Macromolecules, 25(12), 3232-3236 (1992).
26. H. Witte and W. Seelinger, Liebigs Ann. Chem., 996-1009 (1974).
27. H. A. A. Rasoul, D. B. Obuchowski, D. L. Trumbo, B. M. Culbertson, and Y. Xue, Oxazoline Hydrolysis, Synthesis and Polymerization of a New Oxazoline Methacrylate, PP. 871-872 (1997).
The prior art fails to disclose chemical compositions, monomeric or polymeric having both the cyclic imino ether and the acetoacetamide, acetoacetenilide or acetoacetate residues on the same molecule.
The novel compound of this invention has the following formula: 
wherein R is an alkyl group containing 1-5 carbon atoms or an aryl, substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl, alkylether-aryl or O; R1 and R2 are hydrogen or a methyl group; X is O, NH, NRxe2x80x2 wherein Rxe2x80x2 is an alkyl group containing 1-5 carbon atoms, or Oxe2x80x94Rxe2x80x3 or NRxe2x80x3 wherein Oxe2x80x94Rxe2x80x3 is O-alkyl-O or O-alkyl, NRxe2x80x3 is O-alkyl-ONH, 
wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.
The compounds of this invention are monomers which may be polymerized or copolymerized, via cationic, ring-opening polymerization of the cyclic imino ether residues, producing polymers with pendant acetoacetamide, acetoacetanilide and/or acetoacetate groups. Polymers of the aforesaid type may be readily crosslinked, via a variety of reactions as explained in the background art, to produce crosslinked materials useful in coatings, adhesives, and other applications. Further, these monomers and polymers are shown to readily form metal complexes with a variety of metal salts, giving in many cases, highly colored monomer-metal or macromolecular-metal complexes.
Referring to the previous formula, in the instance where R is aryl, X is NH, R1 and R2 are H and n is 0, this compound can be readily prepared by reacting an aminophenyl oxazoline with diketene. In the instance where R is aryl, X is NH, R1 and R2 are H and n is 1,2-(4-aminophenyl) oxazine was reacted with diketene. The compound where R is aryl, X is NRxe2x80x2, R1 and R2 are H and n is 0, this compound is prepared by reacting aminobenzonitrile with an alkyl iodide to obtain an alkylaminobenzonitrile which is treated with ethanolamine to obtain alkylaminophenyl oxazoline. The resulting oxazoline compound is subsequently treated with 2,2,6-trimethyl-1,3-dioxin-4-one (TDO). The compound where R is aryl, X is NH, R, R1 and R2 are CH3 and n is 0 is prepared by reacting ethylaminobenzoate with methylaminopropanol to yield a dimethyl derivative of aminophenyl oxazoline with the resulting oxazaline treated with TDO. The compound where R is alkyl, X is alkyl, R1 and R2 are hydrogen and n is 0 is prepared by reacting an alkylamino alkylnitrile with ethanolamine to obtain alkylamino alkyloxazoline which is subsequently treated with TDO. As to the compound where R, R1, R2 and n are as immediately and previously described but X is O-alkyl, it is obtained by reacting hydroxyalkyl oxazoline and TDO. In those instances where R is aryl, R1 and R2 are hydrogen, n is 0 and X is O-alkyl-O, O-alkyl-CNH or 
the following procedures were employed. Where X is O-alkyl-O, hydroxy-alkylphenyl oxazoline was reacted with TDO; where X is O-alkyl-CONH aminophenyl oxazoline was reacted with an alkyllactone resulting in a hydroxyalkyl substituted amide of the oxazoline compound which is subsequently treated with TDO; where X is 
aminophenyl oxazoline was treated with an alkylene carbonate to obtain an intermediate carbamate deriviative which is subsequently treated with diketene.
To synthesize substituted aryl oxazolines, a substituted aminobenzonitrile such as methyl substituted aminobenzonitrile is reacted with 2-aminoethanol in the presence of a zinc acetate catalyst as set forth in Example 1 to provide an amino and methyl substituted phenyloxazoline. The resulting substituted phenylaxazoline is reacted with diketene in the manner of Example 4 to produce the desired substituted aryl oxazoline. As indicated, the substituents on the phenyl group can be alkyl and other functionalties can include nitro and hydroxyl.
To prepare the compounds of general formula where R is heteroaryl, a hetero group of the formula: 
is reacted with 2-aminoethanol as previously described to result in a compound of the formula: 
which is subsequently reacted with diketene. In the foregoing formula X=sulfur, oxygen, or NH or NR where R is alkyl and Y=hydrogen, bromine, chlorine, iodine fluorine, amino or hydroxyl.
To prepare compounds of the general formula where R is alkyl-aryl, a compound of the formula: 
is reacted with 2-aminoethanol as previously described to result in: 
which is subsequently heated with diketene to produce the desired alky-aryl substituted or unsubstituted acetoacetoxazoaline. In this instance X=hydrogen, carboxyl, halogen, alkyl or aryl.
To synthesize compounds of the general formula where R is alkylether-aryl, a hydroxybenzonitrile is reacted with 2-aminoethanol as previously described to result in a hydroxy substituted phenyloxazoline. This intermediate oxazoline is reacted with, for example ethylene oxide, to produce a compound of the formula: 
which is further reacted with diketene to produce the desired alkylether-aryl substituted acetoacetate oxazoline.
The term xe2x80x9calkylxe2x80x9d as used herein means an alkyl group having 1-5 carbon atoms.